Surface-active incrustation inhibitor



Patented Sept. 1, 1942 UNITED STATES PATENT OFFICE SURFACE-ACTIVEINCRUSTATION INHIBITOR Rudolph S. Bley', Milligan College, Team,assignor to North American Rayon Corporation, New York, N. Y., acorporation of Delaware No Drawing.

Application January 29, 1940,

Serial No. 316,277

11 Claims.

This is a continuation in part of my application Serial No. 233,826,filed- October 7, 1938.

In the manufacture of cellulosic products, such as filaments, threadsand the like, a viscose solution is continuously extruded through theminute orifices of a spinneret into a coagulating or setting bath.However, since the introduction of the viscose process great troubleshave been and are still experienced as far as continuous spinning isconcerned due to impurities, such as, for example, precipitatedcellulose particles, sulphur and resin particles, zinc compounds, etc.,present in either the viscose solution or the spin bath. Theseimpurities gradually contaminate the spinnerets, clog and reduce thewidths of the spinneret orifices with the result that filaments ofuneven thickness are obtained. If contamination proceeds the individualfilaments start to tear and occasion interruption of the spinningprocess.

Cation-active compounds are surface-active compounds which carry in thecation a hydro- They are stability in acid spin baths they are unable toprevent the incrustation of spinnerets and spinneret orifices.

Incrustation inhibitors, in accordance with the present invention, maybe prepared from sulphides derived from monosaccharides of the ketose oraldose type containing 5 or 6 carbon atoms. These sugar sulphides may beprepared from glucose, galactose, fructose, xylose, arabinose, mannose,rhamnose, ribose, talose, etc.

I have found that the contamination of spinnerets and clogging oi,spinneret orifices may be substantially overcome by spinning viscosesolutions in the presence of cation-active monosaccharide derivativeshaving the general structure:

R1 C,.(OH)niH,-+2-SR2 in which n is 5 or 6, R1 is a higher aliphaticradical having 8' or more carbon atoms, R2 represents an aliphatic Oraromatic radical, and Ac,

represents an innocuous anion, such as an OH group or a negative acidradical. R2 may also represent the radical in this structure C11. (OH)n-lHn +2 These inhibitors may be prepared by reacting plain or mixedsulphides of monosaccharides with alkyl, aralkyl or aryl halides inconventional manner in accordance with the following equation:

Although these cation-active incrustation inhibitors may formcorresponding bases in viscose solutions and salts in acid spin baths,they retain their surface-activity and, thus their property ofsubstantially preventing incrustations on prolonged spinning. If verysmall amounts of these cation-active compounds are,

added to viscose solutions or spin baths the physical characteristicssuch as strength, plasticity, lustre, etc., of regenerated celluloseproduced therefrom or therein, respectively, remain unaltered. Uponincreasing the amount of incrustation inhibitor in a given viscosesolution or spin bath, the regenerated cellulose produced therefrom ortherein, respectively, may alter its physical characteristics, 1. e., itmay acquire a soft-lustre, become more plastic, lose part of itsoriginal strength, etc. For such reasons, the amounts to be added toviscose solutions or spin baths must be predetermined byexperimentation. Additions of about 0.3 to 5.0 grams per liter ofviscose solution are generally sufiicient to allow continuous spinningwithout substantially affecting the cellulose threads or films.

inherent physical characteristics of regenerated Although thesecation-active incrustation inhibitors improve the spinning of anyconventional viscose solution or spin bath, I have found that they areespecially valuable as additions to zinc-bearing spin baths. i. e., spinbaths containing a soluble zinc compound, for example, zinc sulphate,since these baths have a great tendency to incrustate metallicspinnerets. I am well aware, that cation-active glucyl amines, etc.,have been heretofore prepared"(vide U. S. Patents Nos. 2,016,956;2,060,- 850; 2,060,851) as wetting agents. However, this prior art doesnot disclose the prevention of incrustations by means of cation-activecompounds.

Examples of suitable incrustation inhibitors are: methyl-fructyl-octylsulphonium chloride,

ethyl-fructyl-octyl sulphonium chloride, methylglucyloctyl sulphoniumbromide, methyl-glucyldodecyl sulphonium bromide, methyl-glucyl-dodecylsulphonium hydroxide, ethyl-glucyl-dodecyl sulphonium sulphate,methyl-glucyl-cetyl sulphonium bromide, phenyl-glucyl-dodecyl sulphoniumbromide, benzyl-glucyl-dodecyl bromide, propyl-glucyl-octyl sulphoniumiodide, methyl-galactyl-octyl sulphonium bromide, ethyl-galactyl-octylsiflphonium methyl-sulphate, etc. However, I wish to emphasize that thepresent invention is not limited to the compounds enumerated above,since any cation-active compound having the structure set forth abovemay be used provided it is sufficiently soluble and stable in viscosesolutions and or acid spin baths to furnish surface-active cationstherein.

Example I About 0.1 to 5 grams of methyl-glucyl-dodecyl sulphoniumbromide is added to one liter of a conventional acid spin bath. When aviscose solution is extruded therein through the fine oridoes of acorrosion-resistant spinneret (for example a platinum alloy spinneret)the incrustation of the spinneret orifices is substantially inhibited.

Example II Viscose filaments are spun in the presence of a small amountof ethyl-glucyl-dodecyl sulphonium bromide with the result that thespinneret orifices remain clean for long periods of time.

Example III About 0.1 to 5 grams of methyl-glucyl-dodecyl sulphoniumbromide is added to one liter of a conventional viscose spinningsolution. When this solution is extruded into an acid spin bath to formfilaments therein the spinnerets, submergedin the spin bath, remainsubstantially free from incrustations.

Example IV substantially stable, cation-active monosaccha- 3 ridederivative having the structure:

in which n is a number selected from the group consisting of 5 and 6,'R1is a higher aliphatic radical having at least 8 carbon atoms, Rzrepresents a radical selected from the group consisting of alkyl,aralkyl and aryl radicals, and Ac represents a substituent selected fromthe group consisting of OH and negative acid radicals, wherebyincrustation of the spinneret during the spinning operation issubstantially inhibited. I

2. An acid viscose spin bath, for coagulating viscose filaments therein,containing a dissolved,

substantially stable, cation-active monosaccharide derivative having thestructure:

in which n is a number selected from the group consisting of 5 and 6, R1is a higher aliphatic radical having at least 8 carbon atoms, R2represents an alkyl radical, and Ac represents a substituent selectedfrom the group consisting of 0H and negative acid radicals, wherebyincrustation of the spinneret during the spinning operation issubstantially inhibited.

3. An acid viscose spin bath, for coagulating viscose filaments therein,containing a dissolved, substantially stable, cation-activemonosaccharide derivative having the structure:

Ac in which n is a number selected from the group consisting of 5 and 6,R1 is a higher aliphatic radical having at least 8 carbon atoms, R2represents an aralkyl radical, and Ac represents a substituent selectedfrom the group consisting of OH and negative acid radicals, wherebyincrustation of the spinneret during the spinning operation issubstantially inhibited.

4. An acid viscose spin bath, for coagulating viscose filaments therein,containing a dissolved, substantially stable, cation-activemonosaccharide derivative having the structure:

in which n is a number selected from the group consisting of 5 and 6, R1is a higher aliphatic radical having at least 8 carbon atoms, R2represents an aryl radical, and Ac represents a substituent selectedfrom the group consisting of OH and negative acid radicals, wherebyincrustation of the spinneret during the spinning operation issubstantially inhibited.

hing operation is substantially inhibited.

6. An acid viscose spin bath containing a watersoluble zinc compound anda dissolved, substantially stable cation-active monosaccharidederivative having the structure: I

in which n is a number selected from the group consisting of 5 and 6, R1is a higher aliphatic radical having at least 8 carbon atoms, R2represents a radical selected from the group cons sting operation issubstantially inhibited.

7. An acid viscose spin bath containing a water soluble zinc compoundand a dissolved, substantially stable cation-active, monosaccharidederivative having the structure:

I RI 0 "(0K) n-1He+z 5 3: Ac in which n is a. number selected from thegroup consisting of 5 and 6, R1 is a higher aliphatic radical having atleast 8 carbon atoms, R: represents an alkyl radical, and Ac representsa substituent selected from the group consisting of 0H and negative acidradicals, whereby incrustation of the spinneret during the spinningoperation is substantially inhibited.

8. An acid viscose spin bath containing a watersoluble zinc compound anda dissolved, substantially stable cation-active monosaccharide de-vrivative having the structure:

' i /Bi in which n is a number selected from the group 30 solvedmethyl-glucyl-dodecyl sulphonium bro consisting of 5 and 6, R1 is ahigher aliphatic radical having at least 8 carbon atoms, R: representsan aralkyl radical, and Ac represents a substituent selected from thegroup consisting of OH and negative acid radicals, whereby incrustationoi the s'pinneret during the spinning operation is substantiallyinhibited.

9. An acid viscose spin bath containing a water-soluble zinc compoundand a dissolved,

substantially stable cation-active monosaccharide derivative having thestructure:

/Ri Cn(0H).-|H-+:S=R:

. Ac in which n is a number selected from the group consisting of 5 and6; R1 is a higher aliphatic radical having at least 8 carbon atoms, R:represents an aryl radical, and Ac represents a subctituent selectedfrom the group consisting of OH and negative acid radicals, wherebyincrustation;

of the spinneret during the spinning operation is substantiallyinhibited.

10. In the manufacture of viscose yarn wherein a viscose solution isextruded through minute orifices of a metal spinneret into an acidprecipitating bath to form filaments and the like therefrom, the stepwhich comprises spinning the viscose filaments in the presence ormethylglucyl-dodecyl sulphonium bromides 11. An acid viscose spin bathcontaining dismide. v

RUDOLPH S. BLEY.

